Dioxazine compounds and process of making same



Patented Dec. 17, 1935 UNITED STATES vPATENT OFFIE DIOXAZINE COMPOUNDSAND PROCESS OF MAKING SAME Georg Kalischer, Frankfort-on-thc-Main, and

Werner Zerweck,

Frankfort-on-the-Main- Fechenheim, Germany, assignors to General AnilineWorks, Inc., New York, N. Y., a corporation of Delaware No Drawing.Original application July 11, 1933,

Serial No. 679,984. Divided and this application May 26, 1934, SerialNo. 727,834. In Germany July 16, 1932 5 Claims.

Our invention relatesto new dioxazine compounds of the general formulain which both external nuclei may contain further monovalentsubstituents and a process of making the said products.

As is well known, quinone and particularly halogenated quinones condensewith o-a-minoaryl-mercaptans with the formation of dyestuffs of thethiazine series. The condensation of chloranil and one molecularproportion of 2 amino-3methyl--5-phenyl-amino-thiophenol, for example;takes place according to the following equation;-

. CH| c1 7 1 Nil: o 01 (cf. U. S. Patent 1,588,384) 7 It is impossibleto apply this condensation reaction to o-aminophenols and theiralkyl-derivatives, since the corresponding oxazine compounds are notformed but rather the quinone in this case only has an oxidizing effect.

. In accordance with the present invention in contradistinction to thislatter fact o-aminophenols of the benzene or naphthalene series containing a nitro-group in the molecule are capable of the abovecondensation reaction with quinones and halogenated quinones of thebenzene or naphthalene series with the formation of new condensationproducts of the oxaz'ine series. l,4-qui-' nones; which may besubstituted by halogen in the 2- and 5-position, are capable of reactingwith i one or also with two molecular proportions ofnitro-o-aminophenols. For example the condensation of chloranil with oneand two molecular proportions respectively of 5-nitro'-2-aminophe n01yields the following compounds OzN -0 -0 and r I VN- 0-- NO:

respectively.

The nitro-oxazines thus obtainable in a very good yield are intenselycolored compounds which (3H3 Fl +HC1+H=0 s 0 may bevused as pigmentdyestuffs; in part they In order to further illustrate our invention thefollowing examples are given, the parts being by weight and alltemperatures in centigrade degrees; but we wish it, however, to beunderstood that our invention is not limited to the particular productsnor reaction conditions given therein:--

Example 1 A mixture of 24,8 parts of chloranil, 34 parts of5-nitro-2-amino-phenol, 25 parts of anhydrous sodium acetate and about250 parts of alcohol is boiled for some hours in an apparatus providedwith a reflux condenser, the reaction product is V filtered off whilewarm, washed out with alcohol and water and dried. When recrystallizedfrom nitrobenzene the new condensation product represents brightviolet-red crystals of a metallic lustre which dissolve in concentratedsulfuric acid with a brilliant green-bluecolor. The compound correspondsprobably to the following formula:

OaN o N r N o No,

i. e. a dichloro-dinitro-triphen-dioxazine.

Example 2 A mixture of 24.8 parts of chloranil, 67 parts of4-nitro-2-aminophenol-fi-sulfonic acid of 72% strength, parts ofanhydrous sodium acetate, about 300 parts of alcohol and about 25 partsof water is boiled for some hours in an apparatus provided with a refluxcondenser. The precipi- "tate is filtered off by suction, washed withalcohol and dried. This intermediate compound dyes wool from an acidbath brown shades and dissolves'in concentrated sulfuric acid with adull red color, turning after a short time to blue. When pouring thisblue solution into water and adding sodium chloride thereto, adioxazine-dyestuff is obtained which dyes cotton from an acid v bathbrown-orange shades and dissolves in concentrated sulfuric acid with abright blue color. The product corresponds probably with the formula:

IOIN N' O Example 3 NOI A mixture of 24.8 parts of chloranll, 44,2 partsof the sodium salt of 2-amino-4,6-dinitrophenol, 30 parts of sodiumacetateand about 200 parts of alcohol of about 90% strength is boiledfor about 5 hours in an apparatus provided with a reflux condenser. Theformed condensation product which corresponds probably with the formula:

OH O- NH Noll OaN NH O HO Cl NO| N02 (Ill OH HO 'N NO:

V N0: G1

I 2 O N NO:

' OzN N 0 is filtered off, washed out and dried. From nitrobenzene itcrystallizes as bluish red needles melting above 300. It dissolves inconcentrated sulfuric acid with a pure violet-blue color.

We claim:

1. A process for producing dioxazines which comprises acting with twomolecular proportions of a nitro-ortho-aminophenol of the benzene ornaphthalene series on one molecular proportion of a halogenated quinoneof the benzene or naphthalene series.

2. Dioxazine compounds corresponding to the 40 general formula 01 o1I-N[ NO: -NO:

1 in which both external nuclei may contain sulfonic acid groups asfurther monovalent substituents which products are intensely colored.

3. The dichloro-dinitro-triphen-dioxazine of the formula:

' OzN o N which represents when recrystallized from-nitrobenzene brightviolet-red crystals of a metallic lustre which dissolve inconcentratedsulfuric acid with a brilliant green-blue color.

4. The dichloro-dinitro-triphen-dioxazine-disulfonic acid of theformula:

OzN N O O N NO:

which dissolves in concentrated sulfuric acid with 7 a bright blue colorand dyes cotton from an acid which dissolves in concentrated sulfuricacid with bath brown-orange shades. a pure violet-blue color andcrystallizes from 5. The dichloro-tetra-nitro-triphen-dioxazinenitrobenzene as bluish red needles melting above of the formula 300 C.

5 GEORG KALISCHER. 5

WERNER ZERWECK.

